JP2014514411A - Method for converting solid biomass material - Google Patents

Abstract

(A) in the catalytic cracking reactor, the solid biomass material and the fluid hydrocarbon feed are contacted with a catalytic cracking catalyst at a temperature above 400 ° C. to produce one or more cracked products; (b) step ( separating one or more decomposition products produced in a) to produce one or more product fractions; (c) hydrodeoxygenating one or more product fractions produced in step (b) Producing a one or more hydrodeoxygenation products; comprising converting a solid biomass material.
[Selection] Figure 1

Description

  The present invention relates to a method for converting solid biomass material, its products, and a method for producing biofuels and / or biochemical substances, and its products.

  As the supply of crude mineral oil has decreased, it has become increasingly important to use renewable energy sources to produce liquid fuels. These fuels from renewable energy sources are often referred to as biofuels.

  Biofuels derived from non-edible renewable energy sources such as cellulosic materials are preferred because they do not compete with food production. These biofuels are also referred to as second generation biofuels, renewable or advanced biofuels. However, most non-edible renewable energy sources are solid biomass materials that are cumbersome to convert to liquid fuel.

  For example, the method of converting solid biomass to hydrocarbons described in WO 2010/062611 requires three catalytic conversion steps. First, contacting the solid biomass with the catalyst in a first riser operating at a temperature in the range of about 50 to about 200 ° C. to produce a first product comprising the first biomass-catalyst mixture and hydrocarbons. Generate (referred to as preprocessing). Thereafter, the first biomass-catalyst mixture is charged to a second riser operating at a temperature in the range of about 200 ° C. to about 400 ° C., thereby a second biomass-catalyst mixture and a hydrocarbon containing hydrocarbon. Finally, the second biomass-catalyst mixture is charged into a third riser operating at a temperature above about 450 ° C. (referred to as deoxygenation and cracking); To produce a third product comprising the catalyst and hydrocarbons consumed thereby. The last step is called conversion to produce fuel or special chemical products. In WO 2010/062611, the possibility of adjusting the biomass to be co-processed in a conventional petroleum refining unit is mentioned. However, the method of WO 2010/062611 is complicated in that each step requires three steps that require its own specific catalyst.

  In WO 2010/135734, catalytic cracking of a biomass feedstock and a refiner feedstock in a purification unit comprising a flow reactor, wherein hydrogen is transferred from the refiner feedstock to carbon and oxygen of the biomass feedstock, A method for co-processing biomass feed and refiner feed in a refining unit is described. In one aspect of WO 2010/135734, the biomass feedstock comprises a plurality of solid biomass particles having an average dimension between 50 and 1000 microns. Incidentally, pretreatment of solid biomass particles may increase brittleness, sensitivity to catalytic conversion (eg, by roasting, firing, and / or heat drying), and / or sensitivity to mixing with petrochemical feedstock. It is further mentioned that it can be done.

  Here, the disadvantages of the processes in the prior art, and in particular the process described in WO 2010/135734, are that one or more products obtained from a fluidized reactor for catalytic cracking are normal feeds. It was recognized for the first time that it contained a much higher concentration of oxygen-containing hydrocarbons than the product obtained by catalytic cracking. These oxygen-containing hydrocarbons, such as ethers, esters, acids, and / or alcohols, can have several drawbacks when present in biofuels and / or biochemical materials. For example, oxygen-containing compounds such as ether can cause peroxide formation under certain circumstances when contacted with air, which can increase the risk of explosion downstream of the reactor. is there. Acids present in the product can cause corrosion downstream of the reactor or, if such acids are included in the biofuel, can cause corrosion in the end user's car engine. Alcohols such as phenols present in the product can be toxic to downstream wastewater purification units. In addition, the ethers or esters present may be undesirable for downstream wastewater purification units as spills can cause groundwater contamination.

International Publication No. 2010/062611 International Publication No. 2010/135734

  It would be an advance in the art to provide a method for converting solid biomass material into biofuel and / or biochemical components without the above disadvantages or one or more disadvantages.

  Such a method has been achieved by the method of the present invention.

Therefore, the present invention
(A) in a catalytic cracking reactor, the solid biomass material and the fluid hydrocarbon feed are contacted with a catalytic cracking catalyst at a temperature greater than 400 ° C. to produce one or more cracked products;
(B) separating the one or more decomposition products produced in step (a) to produce one or more product fractions;
(C) hydrodeoxygenating one or more product fractions produced in step (b) to produce one or more hydrodeoxygenated products;
A method of converting solid biomass material comprising:

Some of these hydrodeoxygenation products are new per se and inventive. Thus, the present invention is also based on the total weight of the composition,
0% to 60% by weight of olefins;
0% to 1% by weight of oxygen-containing hydrocarbons;
-5% by weight to 80% by weight of paraffin;
1% to 60% by weight of cycloparaffin;
-1% by weight to 60% by weight of aromatic compound;
Including:
Also provided is a hydrodeoxygenation product composition comprising biocarbon in the range of 0.02 wt% to 50 wt% based on the total weight of carbon present in the composition.

  One or more hydrodeoxygenation products can be conveniently used as a biofuel component and / or biochemical component, or can be converted to a biofuel component and / or biochemical component.

  The present invention further includes a biofuel component and a biochemical component, respectively, and the biofuel component and biochemical component each include one or more hydrodeoxygenation products obtained in the above method, or the biofuel component and biochemical component. Each chemical component also provides a method for producing biofuels and biochemical materials, respectively, derived from one or more hydrodeoxygenation products obtained in the above method.

Some of these biofuels and / or biochemical substances are novel and inventive in their own right. Therefore, the present invention also provides
(I) normal fuel components;
(Ii) based on the total weight of the composition,
0% to 60% by weight of olefins;
0% to 1% by weight of oxygen-containing hydrocarbons;
-5% by weight to 80% by weight of paraffin;
1% to 60% by weight of cycloparaffin;
-1% by weight to 60% by weight of aromatic compound;
Including:
A hydrodeoxygenation product composition comprising biocarbon in the range of 0.02 wt% to 50 wt% based on the total weight of carbon present in the composition;
Biofuel ingredients including:
A biofuel composition is also provided.

  The method of the invention makes it possible to produce biofuel components and / or biochemical components having a minimum concentration of oxygen-containing hydrocarbons by catalytic cracking of solid biomass material.

  The fluid hydrocarbon co-feed provides hydrogen, which is advantageously used in the removal of oxygen by hydrogen transfer during the catalytic cracking reaction and / or in the hydrodeoxygenation of one or more product fractions of step (b). be able to. While not wishing to be bound by any type of theory, it is believed that the fluid hydrocarbon co-feed helps to minimize the formation of oxygen-containing hydrocarbons.

  The method of the present invention is simple and may require minimal processing steps to convert the solid biomass material into a biofuel component or biochemical component having a low oxygen content. Such biofuel components can be completely replaced.

  Furthermore, the method of the present invention can be easily carried out in existing purification equipment.

  Furthermore, the method of the present invention does not require complex operation and may not require, for example, a premixed composition of solid biomass material and catalyst.

  Thus, the method of the present invention also provides a more direct route to second generation renewable or advanced biofuels and / or biochemical materials by catalytic cracking of solid biomass material.

FIG. 1 shows a schematic diagram of a first process according to the invention. FIG. 2 shows a schematic diagram of a second process according to the invention.

  In step (a) of the method, in the catalytic cracking reactor, the solid biomass material and the fluid hydrocarbon feed are contacted with a catalytic cracking catalyst at a temperature higher than 400 ° C. to produce one or more types of cracked products. Let

  Solid biomass material is understood in the context of the present invention as a solid material obtained from a renewable source. A renewable source is understood in the context of the present invention as a composition of biogenic material as opposed to a composition of material obtained or derived from petroleum, natural gas or coal. While not wishing to be bound by any type of theory, such materials obtained from renewable sources contain carbon-14 isotopes with an abundance of about 0.0000000001%, based on the total number of moles of carbon. May be.

  Preferably, the renewable source is a composition of materials of cellulosic or lignocellulosic origin. Any solid biomass material can be used in the method of the present invention. In a preferred embodiment, the solid biomass material is not a material used for food production. Examples of preferred solid biomass materials include plant materials obtained from aquatic plants and algae, agricultural and / or forest waste and / or paper waste and / or municipal waste.

  Preferably, the solid biomass material comprises cellulose and / or lignocellulose. Examples of suitable cellulose and / or lignocellulose containing materials include grains such as corn stover, soybean stover, corn cobs, rice straw, rice husk, oat husk, corn fiber, wheat, barley, rye, and oat straw. Agricultural waste such as potatoes; turf; forest products and forest residues such as wood-related materials such as wood and sawdust; waste paper; sugar residues such as bagasse and beet pulp; or mixtures thereof. More preferably, the solid biomass material is selected from the group consisting of wood, sawdust, firewood, turf, bagasse, corn stover, and / or mixtures thereof.

  The solid biomass material may allow improved process operability and economy through drying, torrefaction, steam explosion, particle size reduction, densification, and / or pelletization prior to contact with the catalyst. it can.

  Preferably, the solid biomass material in step (a) is a heat-dried solid biomass material. In a preferred embodiment, the method of the present invention comprises the step of heat-drying the solid biomass material at a temperature higher than 200 ° C. to obtain a heat-dried solid biomass material, which is contacted with the catalytic cracking catalyst in step (a). it can. The terms “heat drying” and “heat drying” are used interchangeably herein.

  “Torrefying” or “torrefaction” means, in the present invention, a solid biomass material in an oxygen-poor, preferably oxygen-free atmosphere, in the substantial absence of a catalyst. It is understood that the treatment is performed at a temperature in the range of 200 ° C. to 350 ° C. An oxygen-poor atmosphere is understood as an atmosphere containing 15% or less oxygen, preferably 10% or less oxygen, more preferably 5% or less oxygen. An oxygen free atmosphere is understood to be heat drying in the substantial absence of oxygen.

  Heat drying of the solid biomass material is preferably performed at a temperature higher than 200 ° C., more preferably at a temperature of 210 ° C. or higher, even more preferably at a temperature of 220 ° C. or higher, even more preferably at a temperature of 230 ° C. or higher. Furthermore, the heat drying of the solid biomass material is preferably performed at a temperature of less than 350 ° C., more preferably at a temperature of 330 ° C. or less, even more preferably at a temperature of 310 ° C. or less, and even more preferably at a temperature of 300 ° C. or less.

  Heat drying of the solid biomass material is preferably performed in the substantial absence of oxygen. More preferably, the heat drying is performed under an inert atmosphere containing an inert gas such as nitrogen, carbon dioxide and / or water vapor; and / or a gaseous hydrocarbon such as hydrogen, methane and ethane, or The reaction is performed in a reducing atmosphere in the presence of a reducing gas such as carbon oxide.

  The heat drying process can be performed in a wide range of pressures. However, preferably, the heat drying step is performed at atmospheric pressure (approximately 1 bar, corresponding to approximately 0.1 MPa).

  The heat drying step can be performed batchwise or continuously. When operating in a batch mode, the heat-drying reactor can be filled with solid biomass material, after which the solid biomass material in the heat-drying reactor is at a heat-drying temperature in the range of 1 minute to 12 hours. Heat for a time, more preferably for a time ranging from 30 minutes to 8 hours, most preferably for a time ranging from 1 to 6 hours. The heat drying reactor can then be cooled and emptied to start a new cycle.

  For continuous operation, for example, Thermya's TORSPYD® process (where the flow of solid biomass material flows from top to bottom in the reactor column and from the bottom to the top of the reactor column) Can be used). The temperature of the reactor column gradually increases from top to bottom. The residence time of the solid biomass material in the heat drying reactor is 0.5 minutes or more, more preferably 5 minutes or more, most preferably 15 minutes or more, 2 hours or less, more preferably 1 hour or less, most preferably 45. It may be in the range of minutes or less.

  The heat-dried solid biomass material has a higher energy density, a higher mass density, and greater fluidity and is therefore easier to transport, pelletize, and / or store. Since it is more brittle, it can be easily ground with smaller particles.

  Preferably, the heat-dried solid biomass material is 10 wt% or more, more preferably 20 wt% or more, most preferably 30 wt% or more, 60 wt% or less, more preferably 50 wt%, based on the total weight of the dry matter. It has an oxygen content in the range of up to weight percent oxygen.

  Heated dry gas may be generated during heat drying of the solid biomass material. These heated drying gases can include carbon monoxide and carbon dioxide, but can also include volatile fuels such as methane, ethane, ethene, and / or methanol. In a preferred embodiment according to the present invention, these volatile fuels are recovered from the heated dry gas and recycled as fuel to the process to at least part of the heat for heat drying and / or decomposition in step (a). give. In a further aspect, carbon monoxide and / or carbon dioxide can be recovered from the heated drying gas and recycled to provide an inert or reducing atmosphere for heat drying.

  In a further preferred embodiment, the optional heat drying or heat drying step further comprises drying the solid biomass material prior to heat drying such solid biomass material. In such a drying step, the solid biomass material is preferably in the range of 0.1 wt% to 25 wt%, more preferably 5 wt% to 20 wt%, most preferably solid biomass material. Dry until it has a moisture content in the range of 5% to 15% by weight. For practical purposes, moisture content can be measured by the ASTM E 1756-01 standard test method for measuring total solids in biomass. In this method, weight loss during drying is a measure of the original moisture content.

  Preferably, the solid biomass material in step (a) is a finely divided solid biomass material. A finely divided solid biomass material is understood in the present invention as a solid biomass material having a particle size distribution having an average particle size in the range of 5 μm to 5000 μm as measured using a laser scattering particle size distribution analyzer. The In a preferred embodiment, the method of the present invention includes the step of reducing the particle size of the solid biomass material, optionally before or after the solid biomass material is heat dried. Such a particle size reduction process can be particularly advantageous, for example, when the solid biomass material comprises wood or heat-dried wood. Optionally, the particle size of the heat-dried solid biomass material can be reduced by any method known to those skilled in the art to be suitable for this purpose. Suitable methods for reducing the particle size include grinding, milling, and / or powdering. The particle size can be reduced using, for example, a ball mill, hammer mill, (knife) shredder, cutting machine, knife grid, or cutter.

  Preferably, the solid biomass material has an average particle size of 5 μm (microns) or more, more preferably 10 μm or more, even more preferably 20 μm or more, most preferably 100 μm or more, 5000 μm or less, more preferably 1000 μm or less, most preferably It has a particle size distribution that is in the range of 500 μm or less.

  In one particularly preferred embodiment, the solid biomass material has a particle size distribution with an average particle size of 100 μm or more in order to avoid blockage of the pipelines and / or nozzles. Most preferably, the solid biomass material has a particle size distribution with an average particle size of 3000 μm or less so as to allow easier injection into the riser reactor.

  In another preferred embodiment, the solid biomass material has a particle size distribution with an average particle size of 2000 μm or more, more preferably 2500 μm or more, and most preferably 3000 μm or more. As described in more detail herein below, the process of the present invention can be carried out such that a longer residence time is obtained in the catalytic cracking reactor for the solid biomass material. Such a longer residence time makes it possible to advantageously use a solid biomass material with larger particles. Solid biomass materials with larger particles require less energy to produce. For practical purposes, in this case, the solid biomass material has a particle size distribution with an average particle size of 2 cm or less, more preferably 1 cm or less, most preferably 5000 μm or less. The process of this embodiment is novel and inventive in itself, so the present invention further provides for the catalytic cracking catalyst to convert the solid biomass material and the fluid hydrocarbon feed at temperatures above 400 ° C. in a catalytic cracking reactor. Providing a method for converting a solid biomass material, wherein the solid biomass material has a particle size distribution having an average particle size of 2000 μm or more, wherein the solid biomass material has a particle size distribution having an average particle size of 2000 μm or more. Options for such processes are further described herein above and below.

  For practical purposes, the particle size distribution and average particle size of the solid biomass material is determined according to the ISO 13320 method entitled “Particle Size Analysis—Laser Diffraction Method”, preferably a laser scattering particle size distribution analyzer, Can be determined using Horiba LA950.

  Thus, preferably, the method of the present invention reduces the particle size of the solid biomass material, optionally before and / or after heat drying, to give 5 microns or more, more preferably 10 microns or more, most preferably 20 microns or more. To produce a particle size distribution having an average particle size in the range of 2 cm or less, more preferably 5000 μm (microns) or less, more preferably 1000 μm or less, most preferably 500 μm or less, and micronized and optionally heat dried Producing a solid biomass material.

  In an optional aspect, the particle size reduction of the optionally heat-dried solid biomass material may be suspended in a hydrocarbon-containing liquid to improve processability and / or avoid pulverization. To do. In one preferred embodiment, the suspension of solid biomass particles in such hydrocarbon-containing liquid is a first that reduces the particle size of the solid biomass material to produce a first particulate product comprising solid biomass particles. The first particulate product is suspended in the hydrocarbon-containing liquid, and the suspended first particulate product containing solid biomass particles suspended in the hydrocarbon-containing liquid is obtained. A mixing step to produce; and a suspended second particulate production comprising solid biomass particles suspended in a hydrocarbon-containing liquid by further reducing the particle size of the suspended first particulate product A second particle size reduction step to produce a product.

  Preferably, at least 80% by weight of the first particulate product has a particle size of 300 μm or less, and at least 80% by weight of the second particulate product has a particle size of 100 μm or less.

  Preferably, the hydrocarbon-containing liquid is straight run (atmospheric pressure) gas oil, flash distillate, vacuum gas oil (VGO), coker gas oil, gasoline, naphtha, diesel, kerosene, atmospheric residue (long residue), and vacuum. Residue (short residue) and / or mixtures thereof. Most preferably, the hydrocarbon-containing liquid comprises gasoline, naphtha, diesel, kerosene, and / or mixtures thereof.

  In one aspect, the fluid hydrocarbon co-feed described herein below is used as the hydrocarbon-containing liquid.

  In a preferred embodiment, the optionally pulverized and optionally heat dried solid biomass material is dried prior to feeding to the riser reactor. Thus, if the solid biomass material is heat dried, it can be dried before and / or after heat drying. When dried prior to use as feed to the riser reactor, the solid biomass material is preferably in the range of 50 ° C to 200 ° C, more preferably 80 ° C to 150 ° C. Dry at temperature. The optionally pulverized and / or heat-dried solid biomass material is preferably dried for a time in the range of 30 minutes to 2 days, more preferably in the range of 2 hours to 24 hours.

  In addition to the optionally pulverized and / or heat-dried solid biomass material, a fluid hydrocarbon feed (also referred to herein as a fluid hydrocarbon co-feed) is contacted with the catalytic cracking catalyst in the catalytic cracking reactor. .

  A hydrocarbon feed is understood in the present invention as a feed comprising one or more hydrocarbon compounds. In the present invention, a hydrocarbon compound is understood to be a compound containing and preferably consisting of both hydrogen and carbon. A fluid hydrocarbon feed is understood as a non-solid hydrocarbon feed in the present invention. The fluid hydrocarbon co-feed is preferably a liquid hydrocarbon co-feed, a gaseous hydrocarbon co-feed, or a mixture thereof. The fluid hydrocarbon co-feed can be fed to a catalytic cracking reactor (preferably a riser reactor) in a substantially liquid state, a substantially gaseous state, or a partially liquid and partially gaseous state. it can. When introduced into the catalytic cracking reactor in a substantially or partially liquid state, the fluid hydrocarbon co-feed is preferably vaporized upon introduction, preferably in the gaseous state in the catalytic cracking catalyst and / or solids. Contact with biomass material.

  The fluid hydrocarbon feed may be any non-solid hydrocarbon feed known to those skilled in the art to be suitable as a feed for a catalytic cracking reactor. Fluid hydrocarbon feedstocks include, for example, conventional crude oil (sometimes referred to as petroleum or mineral oil), non-conventional crude oil (ie, oil produced or harvested using techniques other than traditional oil well processes) ) Or renewable oils (ie oils derived from renewable sources such as pyrolysis oils, vegetable oils and / or products of biomass liquefaction processes), Fischer-Tropsch oils (sometimes also synthetic oils) And / or a mixture of any of these.

  In one aspect, the fluid hydrocarbon feed is preferably derived from conventional crude oil. Examples of conventional crudes include West Texas Intermediate, Brent, Dubai-Oman, Arabian Light, Midway Sunset, or Tapis crude.

  More preferably, the fluid hydrocarbon feed preferably comprises a fraction of conventional crude oil or renewable oil. Preferred fluid hydrocarbon feed materials include straight run (atmospheric pressure) light oil, flash distillate, vacuum light oil (VGO), coker light oil, diesel, gasoline, kerosene, naphtha, liquefied petroleum gas, atmospheric residue (long residue). ), And vacuum residue (short residue), and / or mixtures thereof. Most preferably, the fluid hydrocarbon feed comprises long residue, vacuum gas oil, or a mixture thereof.

  In one aspect, the fluid hydrocarbon feed is preferably measured by distillation according to ASTM D86, each entitled “Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure” and “Petroleum Product at Depressurization”. It has a 5 wt% boiling point of 100 ° C. or higher, more preferably 150 ° C. or higher at a pressure of 1 bar absolute pressure (0.1 MPa) as measured by ASTM-D1160 entitled “Standard Test Method for Distillation”. An example of such a fluid hydrocarbon feed is vacuum gas oil.

  In the second aspect, the fluid hydrocarbon feed is preferably measured by distillation according to ASTM D86, each entitled “Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure”, and “Petroleum Oil at Depressurization”. 5 weights of 200 ° C. or more, more preferably 220 ° C. or more, most preferably 240 ° C. or more at a pressure of 1 bar absolute pressure (0.1 MPa) as measured by ASTM D1160 entitled “Standard Test Method for Product Distillation” % Boiling point. An example of such a fluid hydrocarbon feed is long residue.

  In a further preferred embodiment, 70% or more, preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more by weight of the fluid hydrocarbon feedstock is “petroleum product at atmospheric pressure”. 1 bar absolute pressure (0) as measured by distillation based on ASTM D86 entitled “Standard Test Method for Distillation of Oil” and as measured by ASTM D1160 entitled “Standard Test Method for Distillation of Petroleum Products at Reduced Pressure”. .1 MPa) at a pressure of 150 ° C. to 600 ° C.

  The composition of the fluid hydrocarbon feed may vary widely. The fluid hydrocarbon feed may include, for example, paraffins, naphthenes, olefins, and / or aromatics.

  Preferably, the fluid hydrocarbon feed is in the range of 50 wt% or more, more preferably 75 wt% or more, most preferably 90 wt% or more and 100 wt% or less, based on the total weight of the fluid hydrocarbon feedstock. Includes compounds composed solely of carbon and hydrogen.

  Preferably, the fluid hydrocarbon feed is 1 wt% or more paraffin, more preferably 5 wt% or more paraffin, most preferably 10 wt% or more paraffin, preferably 100 wt%, based on total fluid hydrocarbon feedstock. It contains no more than wt% paraffin, more preferably no more than 90 wt% paraffin, most preferably no more than 30 wt% paraffin. Paraffin is understood as both linear, cyclic and branched paraffin.

  In other aspects, the fluid hydrocarbon feed comprises or consists of a paraffinic fluid hydrocarbon feed. Paraffinic fluid hydrocarbon feed, as used herein, is at least 50 wt.% Paraffin, preferably at least 70 wt.%, Most preferably at least 90 wt.%, Based on the total weight of the fluid hydrocarbon feed. It is understood as a fluid hydrocarbon feed with a range of paraffins up to 100% by weight of paraffin.

  For practical purposes, the paraffin content of all fluid hydrocarbon feedstocks with an initial boiling point of at least 260 ° C. is determined from “rubber extenders and processing oils from clay-gel absorption chromatography and other petroleum and other petroleum-derived materials. Standard test method for characteristic groups in oil "ASTM method D2007-03 (where the amount of saturates represents the paraffin content). For all other fluid hydrocarbon feeds, the paraffin content of the fluid hydrocarbon feed is PJ Schoenmakers, JLMM Oomen, J. Blomberg, W. Genuit, G. van Velzen, J., Chromatogr. A, 892 ( 2000), p. 29 et seq., And can be measured by comprehensive multidimensional gas chromatography (GC × GC).

  Examples of such paraffinic fluid hydrocarbon co-feed materials include so-called Fischer-Tropsch derived hydrocarbon streams, such as those described in WO 2007/090884 (incorporated herein by reference), or hydrotreaters. Mention may be made of hydrogen-rich feeds such as products or hydrowaxes. Hydrowax is understood as the bottom fraction of a hydrocracker. Examples of hydrocracking processes that can produce a bottoms fraction that can be used as a fluid hydrocarbon co-feed are described in EP 699225A, EP 649896A, WO 97 / 18278A, EP 705321A, EP 994173A, and US 4851109A. Which are incorporated herein by reference.

  “Fischer-Tropsch derived hydrocarbon stream” means that the hydrocarbon stream is a product from a Fischer-Tropsch hydrocarbon synthesis process, or a hydroprocessing step, ie hydrocracking, hydroisomerization, and / or It is derived from such a product by hydrogenation.

  The Fischer-Tropsch reaction comprises carbon monoxide and hydrogen in the presence of a suitable catalyst, preferably at elevated temperature, for example 125-300 ° C, preferably 175-250 ° C, and elevated pressure, for example 5-100 bar (0 0.5 to 10 MPa), preferably 12 to 80 bar (1.2 to 8.0 MPa), and is converted to longer chain, usually paraffinic hydrocarbons.

n (CO + 2H ₂ ) = (— CH ₂ —) _n + nH ₂ O + heat Carbon monoxide and hydrogen are usually derived from hydrocarbonaceous feedstocks by partial oxidation. Suitable hydrocarbonaceous feedstocks for such partial oxidation include residual fractions from natural gas or gaseous hydrocarbons such as methane, coal, biomass, or crude oil distillation.

  The Fischer-Tropsch derived hydrocarbon stream may suitably be a so-called synthetic crude oil as described, for example, in GB 2386607A, GB 2371807A or EP 0321305A. Other suitable Fischer-Tropsch hydrocarbon streams are derived from the Fischer-Tropsch hydrocarbon synthesis process, optionally in the naphtha, kerosene, light oil, or hydrocarbon fractions having boiling points in the range of hydrotreating steps. It may be.

  Preferably, the Fischer-Tropsch hydrocarbon stream product is obtained by hydroisomerization of hydrocarbons obtained directly in a Fischer-Tropsch hydrocarbon synthesis reaction. The use of hydroisomerized hydrocarbon fractions is advantageous because it contributes to high gasoline yields due to the high content of isoparaffins in such fractions. Hydroisomerization fractions having a boiling point in the kerosene or light oil range can be suitably used as a Fischer-Tropsch derived hydrocarbon stream. Preferably, however, a higher boiling hydroisomerization fraction is used.

  Particularly preferred hydroisomerized hydrocarbon fractions have a T10 wt% boiling point between 350-450 ° C, a T90 wt% boiling point between 450-600 ° C, and a wax content between 5-60 wt%. It is a fraction. Such a fraction is usually referred to as a waxy raffinate. Preferably, the wax content is between 5 and 30% by weight. The wax content is measured by solvent dewaxing at −27 ° C. in a 50/50 vol / vol mixture of methyl ethyl ketone and toluene. Examples of such hydrocarbon streams are commercially available waxy raffinate products sold by Shell MDS (Malaysia), as well as waxy raffinates obtained by the method described in WO 02/070630 or A or EP 0668342B. It is a product.

In a particularly preferred embodiment, the fluid hydrocarbon co-feed is
A fraction of crude oil such as, for example, (normal pressure) gas oil, flash distillate, vacuum gas oil (VGO), coker gas oil, atmospheric residue (long residue), and vacuum residue (short residue); Paraffinic fluid hydrocarbon co-feed materials;
In combination with.

  The weight ratio between the solid biomass material and the fluid hydrocarbon co-feed may vary widely. In order to facilitate co-processing, the weight ratio of fluid hydrocarbon co-feed to solid biomass material is preferably 50/50 (5: 5) or more, more preferably 70/30 (7: 3) or more. Even more preferably, it is 80/20 (8: 2) or more, and still more preferably 90/10 (9: 1) or more. For practical purposes, the weight ratio of fluid hydrocarbon co-feed to solid biomass material is preferably 99.9 / 0.1 (99.9: 0.1) or less, more preferably 95 / 5 (95: 5) or less. The fluid hydrocarbon cofeed and solid biomass material are preferably fed to the catalytic cracking reactor in a weight ratio within the above range.

  The amount of solid biomass material is preferably not more than 30% by weight, more preferably not more than 20% by weight, based on the total weight of solid biomass material and fluid hydrocarbon co-feed present in the feed to the catalytic cracking reactor Most preferably, it is 10 wt% or less, and still more preferably 5 wt% or less. For practical purposes, the amount of solid biomass material present is preferably 0, based on the total weight of solid biomass material and fluid hydrocarbon co-feed present in the feed to the catalytic cracking reactor. .1% by weight or more, more preferably 1% by weight or more.

In a particularly preferred method, the total feed to step (a) is
(1) 0 wt% or more and 99 wt% or less, preferably 0 wt% or more and 20 wt% or less of a paraffinic fluid hydrocarbon co-feed material;
(2) 0 wt% or more and 99 wt% or less, preferably 60 wt% or more and 80 wt% or less, for example, (normal pressure) light oil, flash distillate, naphtha, diesel, kerosene, liquefied petroleum gas, vacuum light oil (VGO), fractions of crude oil such as coker gas oil, atmospheric residue (long residue), and vacuum residue (short residue); and (3) 1 wt% to 35 wt%, preferably 1 wt% Greater than or equal to 20% by weight or less of the solid biomass material described herein or a portion thereof;
including.

  In a preferred embodiment, the fluid hydrocarbon co-feed is 8% or more elemental hydrogen, more preferably 12% by weight or more based on total fluid hydrocarbon co-feed on a dry basis (ie water free basis). Contains a lot of elemental hydrogen. A high content of elemental hydrogen, such as a content of 8% by weight or more, allows the hydrocarbon cofeed to function as an inexpensive hydrogen donor in the catalytic cracking process. A particularly preferred fluid hydrocarbon co-feed with a content of elemental hydrogen above 8% by weight is Fischer-Tropsch derived waxy raffinate. Such a Fischer-Tropsch derived waxy raffinate may comprise, for example, about 85% by weight elemental carbon and 15% by weight elemental hydrogen.

  Without wishing to be bound by any kind of theory, the higher weight ratio of fluid hydrocarbon co-feed to solid biomass material allows the solid biomass material to be more modified by hydrogen transfer reactions.

  Preferably step (a) is carried out in a catalytic cracking unit, more preferably in a fluid catalytic cracking (FCC) unit. Preferably, the catalytic cracking unit includes at least a catalytic cracking reactor and a catalyst regenerator.

  The catalytic cracking reactor used in step (a) may be any catalytic cracking reactor known in the art to be suitable for this purpose, such as, for example, a fluidized bed reactor or a riser reactor. . Most preferably, the catalytic cracking reactor is a riser reactor.

  The fluid hydrocarbon co-feed, and optionally micronized and / or optionally heat-dried solid biomass material, can be mixed prior to introduction into the catalytic cracking reactor, or they can be at the same or different locations. It can be added separately to the catalytic cracking reactor.

  In one aspect, the fluid hydrocarbon co-feed, and optionally the micronized and / or heat dried solid biomass material, are not mixed prior to introduction into the catalytic cracking reactor. In this embodiment, the fluid hydrocarbon co-feed and the solid biomass material can be fed simultaneously (ie, at one location) to the catalytic cracking reactor and optionally mixed at the introduction of the catalytic cracking reactor; Alternatively, the fluid hydrocarbon cofeed and solid biomass material can be added separately (at different locations) to the catalytic cracking reactor. Catalytic cracking reactors, particularly riser reactors, may have a plurality of feed inlet nozzles. Thus, the solid biomass material and the fluid hydrocarbon co-feed are processed in a catalytic cracking reactor by feeding each component through separate feed inlet nozzles, even when both components are not miscible. can do.

  In other aspects, the fluid hydrocarbon co-feed and solid biomass material are mixed prior to introduction into the catalytic cracking reactor to provide a feed mixture comprising the fluid hydrocarbon co-feed and solid biomass material. When mixing the fluid hydrocarbon co-feed and the solid biomass material, the solid biomass material is preferably a biomass material that has been heat dried and micronized as described herein above. The fluid hydrocarbon co-feed and, optionally, micronized and / or heat-dried solid biomass material are mixed in any manner known to those skilled in the art to be suitable for mixing viscous liquids and solids. can do. Preferably, the fluid hydrocarbon co-feed and optionally micronized and / or heat dried solid biomass material are mixed by shaking, stirring, and / or extrusion.

  The feed mixture can be prepared just prior to introduction into the catalytic cracking reactor, or in some cases can be held in a stirred feed vessel before being sent to the catalytic cracking reactor.

  Next, the solid biomass material and the fluid hydrocarbon co-feed are contacted with a catalytic cracking catalyst in a catalytic cracking reactor.

  As indicated above, the catalytic cracking reactor is preferably a riser reactor. Preferably such riser reactor is a riser reactor suitable for fluid catalytic cracking. More preferably, such riser reactor is part of a catalytic cracking unit, more preferably a fluid catalytic cracking (FCC) unit.

  In one preferred embodiment, a suspension of solid biomass material suspended in a fluid hydrocarbon feed is fed to the riser reactor. The options for the fluid hydrocarbon feed are as described herein above.

  In another preferred embodiment, the catalytic cracking reactor is a riser reactor and the solid biomass material is fed to the riser reactor at a location downstream of the location where the fluid hydrocarbon feed is fed to the riser reactor. . Without wishing to be bound by any type of theory, it is believed that hydrogen can be produced by first contacting the fluid hydrocarbon co-feed with a catalytic cracking catalyst. This availability of hydrogen can help reduce coke formation when contacting the solid biomass material with the catalytic cracking catalyst more downstream in the riser reactor.

  In another preferred embodiment, the catalytic cracking reactor is a riser reactor and the solid biomass material is fed to the riser reactor at a location upstream of the location where the fluid hydrocarbon feed is fed to the riser reactor. . While not wishing to be bound by any type of theory, this allows the solid biomass material to be first contacted with a catalytic cracking catalyst; allowing the solid biomass material to be converted to an intermediate oil product. It is believed that this intermediate oil product can be at least partially and preferably fully vaporized prior to quenching the catalytic cracking catalyst by adding a fluid hydrocarbon feed. In addition, supplying solid biomass material upstream of the fluid hydrocarbon feed causes in-situ water production in the upstream portion of the riser reactor, resulting in lower hydrocarbon content in the upstream portion of the riser reactor. Pressure and higher olefin yield can be derived. Furthermore, by supplying the solid biomass material upstream of the fluid hydrocarbon feed, a longer residence time for the solid biomass material is possible, and for this reason a solid biomass material having a particle size distribution with a particle size of 2000 μm or more Can be used.

  In a further aspect, a suspension of solid biomass material suspended in the first fluid hydrocarbon feed is fed to the riser reactor at a first location, and the second fluid hydrocarbon feed is Feed to the riser reactor at a second position downstream of the first position. The options for the first and second fluid hydrocarbon feeds are as described above for the fluid hydrocarbon feeds herein.

  A riser reactor is understood in the context of the present invention as an elongated, preferably substantially tubular reactor suitable for carrying out catalytic cracking reactions. Preferably, the fluid catalytic cracking catalyst flows in the riser reactor from the upstream end to the downstream end of the reactor. The elongated, preferably substantially tubular reactor is preferably oriented substantially vertically. Preferably, the fluid catalytic cracking catalyst flows upward from the bottom of the riser reactor to the top of the riser reactor.

  Examples of suitable riser reactors are described in chapter 3 of the handbook entitled "Fluid Catalytic Cracking technology and operations" by Joseph W. Wilson (published by PennWell Publishing Company (1997)), especially pages 101-112 (for reference). Included in this specification).

  For example, the riser reactor may be a so-called internal riser reactor or a so-called external riser reactor as described herein.

  An internal riser reactor, in the present invention, has a substantially vertical upstream end disposed outside the container and a substantially vertical downstream end disposed inside the container. A good, substantially vertical, preferably substantially tubular reactor is understood. The downstream end of the internal riser reactor located inside the vessel is preferably 30% or more of the total length of the riser reactor, more preferably 40% or more, even more preferably 50% or more, most preferably It constitutes 70% or more. The vessel is preferably a reaction vessel suitable for catalytic cracking reactions and / or a vessel comprising one or more cyclone separators and / or swirl tubes. In the process of the present invention, an internal riser reactor is particularly advantageous because the solid biomass material can be converted to an intermediate oil product (sometimes also referred to as pyrolysis oil). While not wishing to be bound by any type of theory, this intermediate oil product or pyrolysis oil is due to oxygen-containing hydrocarbons and / or olefins that may be present in the intermediate oil product. It is thought that there is a possibility of being more easily polymerized than conventional oils. The total olefin yield can also be increased by reducing the polymerization of the olefin formed. In addition, the intermediate oil product may be more corrosive than conventional oils due to oxygen-containing hydrocarbons that may be present. Furthermore, the internal riser reactor may be less sensitive to erosion by unconverted particles of solid biomass material. By using an internal riser reactor, reducing the risk of clogging due to polymerization and / or reducing the risk of corrosion and / or erosion, thereby increasing safety and equipment integrity Can do.

  An external riser reactor is understood in the present invention as a riser reactor which is preferably arranged outside the vessel. The external riser reactor can preferably be connected to the vessel via a so-called crossover. Preferably, the external riser reactor preferably comprises a substantially vertical riser reactor pipe. Such riser reactor pipe is located outside the vessel. The riser reactor pipe is suitably connected to the vessel, preferably via a substantially horizontal downstream crossover pipe. The downstream crossover pipe preferably has a direction substantially transverse to the direction of the riser reactor pipe. The vessel may suitably be a reaction vessel suitable for catalytic cracking reactions and / or a vessel comprising one or more cyclone separators and / or vortex separators.

  When using an external riser reactor, for example, a handbook entitled "Fluid Catalytic Cracking technology and operations" by Joseph W. Wilson (published by PennWell Publishing Company, (1997)), Chapters 3 to 7 (for reference) It may be advantageous to use an external riser reactor having a bend or low velocity zone at its upper end, as shown in (included herein). The bend and / or the low speed zone may, for example, connect a riser reactor pipe and a so-called crossover pipe.

  A low velocity zone is understood in the context of the present invention preferably as a zone or region in the external riser reactor where the rate of the catalytic cracking catalyst (preferably fluidised) shows a minimum value. The low velocity zone is located, for example, at the most downstream end of the upstream riser reactor pipe, as described above, and the riser reactor pipe extends beyond the connection with the crossover pipe. Storage space may be included. An example of a low speed zone is the so-called “blind tee”.

  Advantageously, a portion of the catalytic cracking catalyst is deposited in the bend or low velocity zone, thereby protecting against catalytic corrosion and / or corrosion and / or erosion by residual solid particles, and oxygen-containing hydrocarbons It has been found that a protective layer against corrosion by can be formed.

  In a preferred embodiment, solid biomass material is fed to the riser reactor in the most upstream half of the riser reactor, more preferably in the most upstream quarter, and even more preferably in the most upstream 1/10. Most preferably, the solid biomass material is fed to the riser reactor at the bottom of the reactor. By adding solid biomass material at the upstream portion of the reactor, preferably at the bottom, in-situ water formation can advantageously occur at the upstream portion of the reactor, preferably at the bottom. In-situ water formation can reduce hydrocarbon partial pressure and reduce secondary hydrogen transfer reactions, thereby obtaining higher olefin yields. Preferably, the hydrocarbon partial pressure is 0.7 to 2.8 bar absolute pressure (0.07 to 0.28 MPa), more preferably 1.2 to 2.8 bar absolute pressure (0.12 to 0.28 MPa). Reduce to range pressure.

  It may be advantageous to also add lift gas at the bottom of the riser reactor. Examples of such lift gases include water vapor, vaporized oil, and / or petroleum fractions, and mixtures thereof. From a practical point of view, water vapor is most preferable as the lift gas. However, using vaporized oil and / or petroleum fraction (preferably vaporized liquefied petroleum gas, gasoline, diesel, kerosene, or naphtha) as the lift gas can allow the lift gas to simultaneously function as a hydrogen donor and reduce coke formation. It may have the advantage that it can be deterred or reduced. In a particularly preferred embodiment, both steam and vaporized oil and / or vaporized petroleum fraction (preferably liquefied petroleum gas, vaporized gasoline, diesel, kerosene or naphtha) are used as lift gas. Most preferably, the lift gas is composed of water vapor.

  If the solid biomass material is fed at the bottom of the riser reactor, it can optionally be mixed with such lift gas before being introduced into the riser reactor.

  If the solid biomass material is not mixed with the lift gas before it is introduced into the riser reactor, it is fed to the riser reactor at the same time (at one and the same location) as the lift gas, and possibly into the riser reactor. It can be mixed at the time of introduction; or it can be fed to the riser reactor separately (at different locations) from the lift gas.

  When both solid biomass material and lift gas are introduced into the bottom of the riser reactor, the lift gas / solid biomass material weight ratio is preferably 0.01: 1 or more, more preferably 0.05: 1 or more. In the range of 5: 1 or less, more preferably 1.5: 1 or less.

  When the solid biomass material is introduced at the bottom of the riser reactor, increasing the residence time of the solid biomass material in that portion of the riser reactor can be increased by increasing the diameter of the riser reactor at the bottom. May be advantageous. Thus, in a preferred embodiment, the riser reactor comprises a riser reactor pipe and a bottom section, the bottom section has a larger diameter than the riser reactor pipe, and the solid biomass material is in the riser reaction within the bottom section. Supply to the vessel. This can advantageously result in improved conversion of solid biomass material and less unconverted solid biomass material particles.

  Where applicable, diameter is understood in the present invention to preferably refer to an inner diameter, for example the inner diameter (ie the inner diameter) of the bottom section or riser reactor pipe. Preferably, the maximum inner diameter of the bottom section of the riser reactor is greater than the maximum inner diameter of the riser reactor pipe.

  The bottom section having a larger diameter may have the form of a lift pot, for example. Accordingly, a bottom section having a larger diameter is also referred to in the present invention as a lift pot or an enlarged bottom section.

  Such an enlarged bottom section is preferably larger in diameter than the diameter of the riser reactor pipe, more preferably in the range of 0.4 to 5 m, most preferably in the range of 1 to 2 m. Have The height of the enlarged bottom section or lift pot ranges from 1 m to 5 m.

  In a further preferred embodiment, the riser reactor can have a diameter that increases in the downstream direction so that an increased volume of gas can be generated during the conversion of the solid biomass material. The increase in diameter is intermittent, giving two or more sections of the riser reactor with a constant diameter so that each preceding section has a smaller diameter than the subsequent sections when going downstream. The diameter increase can be gradual so that the riser reactor diameter gradually increases in the downstream direction; or the diameter increase can be a mixture of gradual and intermittent increases. It can be in the form.

  The length of the riser reactor can vary widely. For practical purposes, the riser reactor is preferably in the range of 10 m or more, more preferably 15 m or more, most preferably 20 m or more, 65 m or less, more preferably 55 m or less, most preferably 45 m or less. Have a length of

  Preferably, the temperature in the catalytic cracking reactor (preferably the riser reactor) is in the range of 450 ° C. or higher, more preferably 480 ° C. or higher, 800 ° C. or lower, more preferably 750 ° C. or lower.

  Preferably, the temperature at the position of supplying the solid biomass material is 500 ° C. or higher, more preferably 550 ° C. or higher, most preferably 600 ° C. or higher, 800 ° C. or lower, more preferably 750 ° C. or lower.

  In some embodiments, the solid biomass material is placed at a position where the temperature in the riser reactor is slightly higher, such as a temperature of 700 ° C or higher, more preferably 720 ° C or higher, even more preferably 732 ° C or higher, 800 ° C. Below, it may be advantageous to supply to a position that is more preferably in the range of 750 ° C. or less. While not wishing to be bound by any type of theory, it is believed that this can result in a faster conversion of solid biomass material to an intermediate oil product.

  Preferably, the pressure in the catalytic cracking reactor (preferably the riser reactor) is 0.5 bar absolute pressure to 10 bar absolute pressure (0.05 MPa to 1.0 MPa), more preferably 1.0 bar absolute pressure. It is the range of thru | or 6 bar absolute pressure or less (0.1 MPa-0.6 MPa).

  When using a riser reactor, preferably the total average residence time of the solid biomass material is 1 second or more, more preferably 1.5 seconds or more, even more preferably 2 seconds or more, preferably 10 seconds or less, preferably Is in the range of 5 seconds or less, more preferably 4 seconds or less.

  The residence time referred to in this patent application is based on the residence of the steam at the outlet conditions, i.e. the residence time is not only the residence time of the specified feed (e.g. solid biomass material) but also the conversion product thereof. Residence time is also included.

  If the solid biomass material has an average particle size of 2000 μm or more, preferably a particle size distribution having a particle size in the range of 100 μm to 1000 microns, the total average residence time of the solid biomass material is most preferably 1 second or more. And preferably in the range of 2.5 seconds or less.

  When the solid biomass material has an average particle size in the range of 30 μm to 100 μm, the total average residence time of the solid biomass material is most preferably in the range of 0.1 second to 1 second.

  The weight ratio of catalyst to feed (ie solid biomass material, and total feed of fluid hydrocarbon feed) (also referred to as catalyst: feed ratio in the present invention) is preferably 1: 1 or more, and more Preferably it is 2: 1 or more, most preferably 3: 1 or more, 150: 1 or less, more preferably 100: 1 or less, most preferably 50: 1 or less.

  The weight ratio of catalyst to solid biomass material (catalyst: solid biomass material ratio) at the position where solid biomass material is fed to the riser reactor is preferably 1: 1 or higher, more preferably 2: 1 or higher, most preferably Is 3: 1 or more, 150: 1 or less, more preferably 100: 1 or less, even more preferably 50: 1 or less, most preferably 20: 1 or less.

  When the fluid hydrocarbon feed is introduced into the riser reactor downstream of the solid biomass material, the fluid hydrocarbon feed preferably has a solid biomass material already greater than or equal to 0.01 seconds, more preferably 0.05. Introduce into the catalytic cracking reactor at a position having a residence time in the range of not less than seconds, most preferably not less than 0.1 seconds, not more than 2 seconds, more preferably not more than 1 second, most preferably not more than 0.5 seconds. be able to.

  In a preferred embodiment, the ratio of the total residence time for the solid biomass material to the total residence time for the fluid hydrocarbon feed (residual solid biomass material: residual hydrocarbon ratio) is 1.01: 1 or higher, more preferably 1 The range is 1: 1 or more and 3: 1 or less, more preferably 2: 1 or less.

  Preferably, the temperature at the location in the riser reactor that supplies the fluid hydrocarbon feed is in the range of 450 ° C. or higher, more preferably 480 ° C. or higher and 650 ° C. or lower, more preferably 600 ° C. or lower. While not wishing to be bound by any type of theory, it is possible to quench the catalytic cracking catalyst by adding a fluid hydrocarbon feed, thus lowering the temperature at the location where it is added to the riser reactor. It is thought that you can.

  Therefore, preferably, the solid biomass material is introduced into the riser reactor at a position having a temperature T1, and the fluid hydrocarbon feed is introduced into the riser reactor at a position having a temperature T2, where the temperature T1 is higher than the temperature T2. . Preferably, both T1 and T2 are 400 ° C. or higher, more preferably 450 ° C. or higher.

  The catalytic cracking catalyst may be any catalyst known to those skilled in the art to be suitable for use in the cracking process. Preferably, the catalytic cracking catalyst comprises a zeolite component. Furthermore, the catalytic cracking catalyst can contain an amorphous binder compound and / or a filler. Examples of the amorphous binder component include silica, alumina, titania, zirconia, and magnesium oxide, or combinations of two or more thereof. Examples of the filler include clay (for example, kaolin).

  The zeolite is preferably a large pore zeolite. Examples of the large pore zeolite include zeolites having a porous crystalline aluminosilicate structure having a porous internal cell structure in which the main axis of the pores above is in the range of 0.62 nm to 0.8 nm. The axis of the zeolite is shown in “Atlas of Zeolite Structure Types”, W.M. Meier, D.H. Olson, and Ch. Baerlocher, 4th revised edition, 1996, Elsevier, ISBN 0-444-10015-6. Examples of such large pore zeolites include FAU or faujasite, preferably synthetic faujasite, such as zeolite Y or X, ultrastable zeolite Y (USY), rare earth zeolite Y (= REY), and rare earth USY (REUSY). ). According to the present invention, USY is preferably used as the large pore zeolite.

  The catalytic cracking catalyst can also include a medium pore zeolite. Medium pore zeolites that can be used in accordance with the present invention include a porous crystalline aluminosilicate structure having a porous internal cell structure with a major axis of pores thereon ranging from 0.45 nm to 0.62 nm. Zeolite. Examples of such medium pore zeolites are of the MFI structure type, eg ZSM-5; MTW type, eg ZSM-12; TON structure type, eg θ-1; and FER structure type, eg ferrier. Light. According to the present invention, ZSM-5 is preferably used as a medium pore zeolite.

  According to other embodiments, blends of large and medium pore zeolites can be used. The ratio of large pore zeolite to medium pore zeolite in the cracking catalyst is preferably in the range of 99: 1 to 70:30, more preferably in the range of 98: 2 to 85:15.

  The total amount of large pore zeolite and / or medium pore zeolite present in the cracking catalyst is preferably in the range of 5% to 40% by weight, more preferably 10% by weight, based on the total mass of the catalytic cracking catalyst. It is in the range of ˜30% by weight, even more preferably in the range of 10% by weight to 25% by weight.

  Preferably, the catalytic cracking catalyst is contacted in a co-current form, preferably with a co-current flow of solid biomass material and optionally a fluid hydrocarbon feed.

  The catalytic cracking of biomass material with the catalytic cracking catalyst described herein is preferably performed in a catalytic cracking unit, preferably a fluid catalytic cracking unit.

In a preferred embodiment, step (a) comprises
Contacting a solid biomass material and a fluid hydrocarbon feed with a catalytic cracking catalyst in a catalytic cracking reactor at a temperature above 400 ° C. to produce one or more cracked products and a consumed catalytic cracking catalyst. A catalytic cracking process comprising:
A separation step comprising separating one or more cracked products from the spent catalytic cracking catalyst;
A regeneration step comprising regenerating the spent catalytic cracking catalyst to produce regenerated catalytic cracking catalyst, heat, and carbon dioxide; and
A recycling step comprising recycling the regenerated catalytic cracking catalyst to the catalytic cracking step;
Including a catalytic cracking process.

  The catalytic cracking step is preferably performed as described herein above.

  The separation step is preferably performed using one or more cyclone separators and / or one or more spiral tubes. A suitable method for carrying out the separation step is in particular 219 of the handbook entitled “Fluid Catalytic Cracking; Design, Operation, and Troubleshooting of FCC Facilities” (Reza Sadeghbeigi, Gulf Publishing Company, Houston, Texas (1995)). ~ 223 pages and handbook "Fluid Catalytic Cracking technology and operations", Joseph W. Wilson, PennWell Publishing Company, (1997), Chapter 3, especially 104-120, and Chapter 6, especially 186-194 (for reference) Included in this specification). The cyclone separator is preferably operated at a speed in the range of 18-80 m / sec, more preferably at a speed in the range of 25-55 m / sec.

  Further, the separation step can further include a stripping step. In such a stripping step, the product absorbed on the consumed catalyst can be recovered by stripping the consumed catalyst before the regeneration step. These products can be recycled and added to the cracked product stream obtained from the catalytic cracking process.

  The regeneration step preferably includes contacting the spent catalytic cracking catalyst with an oxygen-containing gas in a regenerator at a temperature of 550 ° C. or higher to produce regenerated catalytic cracking catalyst, heat, and carbon dioxide. . During regeneration, the coke that may be deposited on the catalyst as a result of the catalytic cracking reaction is burned off to restore the catalytic activity.

The oxygen-containing gas may be any oxygen-containing gas known to those skilled in the art to be suitable for use in the regenerator. For example, the oxygen containing gas may be air or oxygen enriched air. In the present invention, oxygen-enriched air is understood as air containing more than 21% by volume of oxygen (O ₂ ), more preferably air containing more than 22% by volume of oxygen, based on the total volume of air.

  The heat generated in the exothermic regeneration process is preferably used to provide energy for the endothermic catalytic cracking process. Furthermore, the heat generated can be used to heat water and / or generate water vapor. Steam can be used as lift gas elsewhere in the purification facility, for example, in a riser reactor.

  Preferably, the spent catalytic cracking catalyst is regenerated at a temperature in the range of 575 ° C. or higher, more preferably 600 ° C. or higher and 950 ° C. or lower, more preferably 850 ° C. or lower. Preferably, the consumed catalytic cracking catalyst is 0.5 bar absolute pressure to 10 bar absolute pressure (0.05 MPa to 1.0 MPa), more preferably 1.0 bar absolute pressure to 6 bar absolute pressure (0.1 MPa). Regenerate at a pressure in the range of ~ 0.6 MPa).

  The regenerated catalytic cracking catalyst can be recycled to the catalytic cracking process. In a preferred embodiment, a side stream of make-up catalyst is added to the recycle stream to compensate for catalyst loss in the reaction zone and regenerator.

  In step (a) of the method of the present invention, one or more kinds of decomposition products are produced. At least one of the one or more degradation products is then fractionated in step (b) to produce one or more product fractions.

  As indicated herein, the one or more decomposition products may comprise one or more oxygen-containing hydrocarbons. Examples of such oxygen-containing hydrocarbons include ethers, esters, ketones, acids, and alcohols. In particular, the one or more degradation products may contain phenols.

  Preferably, the one or more degradation products produced in step (a) and fractionated in step (b) are 0.01 wt% or more, more preferably 0.1 wt%, based on the total weight of the dry matter. % Or more, even more preferably 0.2% by weight or more, most preferably 0.3% by weight or more, 10% by weight or less, more preferably 5% by weight or less, most preferably 1% by weight or less. Has elemental oxygen content.

  Fractionation can be done by any method known to those skilled in the art to be suitable for fractionating the product from the catalytic cracking reactor. For example, classification can be found in a handbook entitled “Fluid Catalytic Cracking technology and operations” (Joseph W. Wilson, PennWell Publishing Company, (1997)), Chapter 8, especially pages 223-235 (herein incorporated by reference). Inclusive).

  One or more types of decomposition products are preferably obtained as gaseous decomposition products from step (a). These gaseous decomposition products can then be separated into various gaseous and liquid products in one or more fractionation units.

  It has been found that the use of solid biomass material as part of the feed in step (a) can cause further coke formation in a conduit that transports one or more cracked products from the catalytic cracking reactor. . Accordingly, it has been found advantageous in step (b) to use an adiabatic line to transfer one or more cracked products from the catalytic cracking reactor into one or more subsequent fractionation units. Most preferably, a so-called cold wall pipe including a heat insulating portion on the inner pipe surface is used.

  Preferably, the main fractionator is used to cool the gaseous decomposition product obtained from step (a) and to condense the heavy liquid product. The main fractionator preferably comprises a distillation column comprising a bottom section (sometimes referred to as a flash zone) at the bottom of the column; a heavy cycle oil (HCO) section; a light cycle oil (LCO) section; and a top section.

  In the bottom section, the cracked product is preferably cooled by contact with the recycle stream of the fractionator bottom product (sometimes also referred to as the bottom flow pump around). In addition to cooling the gaseous cracked product, the circulating liquid fractionator bottom product can also be advantageously used to wash away residual solid biomass particles.

  To treat the residual solid biomass particles, the bottom section is preferably also fitted with one or more baffle plates, grid fillers, and / or one or more solid biomass particle catchers. Residual solid biomass particles that accumulate in these catchers can be advantageously recycled to step (a). The product obtained from the bottom section at the bottom of the tower is sometimes referred to as slurry oil. Slurry oil is understood in the context of the present invention as a fraction of cracked products, preferably at least 80% by weight, more preferably at least 90% by weight (at 0.1 MPa) boiling above 425 ° C. The slurry oil may still contain solid biomass particles that have not been converted in the catalytic cracking reactor. Such solid biomass particles can be separated from the slurry oil by sedimentation, filtration, and / or electrostatic filtration and advantageously recycled to step (a).

  In the heavy cycle oil (HCO) section, so-called heavy cycle oil can be discharged from the distillation column. In the present invention, the heavy cycle oil is preferably a decomposition product in which at least 80% by weight, more preferably at least 90% by weight (at 0.1 MPa) boils in the range of 370 ° C. to less than 425 ° C. It is understood as a fraction. In a preferred embodiment, at least a portion of this heavy cycle oil is advantageously recycled and used as the fluid hydrocarbon cofeed in step (a).

  When cooling one or more cracked products and recovering the slurry oil and / or heavy cycle oil in the HCO section in the bottom section, the heat of the one or more cracked products is recovered and the process ( It can advantageously be used to preheat the feed in a). For example, one or more of the feed streams for step (a) can be used to cool the circulating liquid fractionator bottom product.

  Further, at least a portion of the heavy cycle oil and / or at least a portion of the slurry oil can be used as fuel to provide heat for the optional heat drying step described herein.

  In the light cycle oil (LCO) section, so-called light cycle oil can be discharged from the distillation column. Light cycle oil (LCO) in the present invention is preferably a cracked product in which at least 80% by weight, more preferably at least 90% by weight (at 0.1 MPa) boils in the range from 221 ° C. to less than 370 ° C. It is understood as a fraction of things. This light cycle oil or part thereof may advantageously be hydrodeoxygenated in step (c) to produce one or more hydrodeoxygenation products, as described in more detail below. it can. Alternatively, at least a portion of the light cycle oil can also be discharged and used directly as a biofuel component and / or biochemical component.

  In the top section of the distillation column, naphtha products and so-called dry gas can be discharged. The naphtha product is preferably a fraction of the decomposition product in which at least 80% by weight, more preferably at least 90% by weight (at 0.1 MPa) of the naphtha product boils in the range from 30 ° C. to less than 221 ° C. It is understood.

  In the context of the present invention, dry gas is preferably understood as a fraction composed of a compound that boils below the boiling point of ethane. The dry gas may include, for example, methane, ethane, ethene, carbon monoxide, carbon dioxide, hydrogen, and nitrogen. Naphtha products can contain fractions that may be useful as biofuel components for gasoline and / or diesel compositions. Preferably, the dry gas is separated from the naphtha product by one or more gas / liquid separators and / or one or more absorbers. Subsequently, if desired, the naphtha product can be debutanized and / or depentanated to remove compounds boiling at temperatures below the butane boiling point and below the pentane boiling point, respectively. At least a portion of the optionally debutanated and / or depentanated naphtha product is advantageously hydrodeoxygenated in step (c) to produce one or more hydrogens, as described in more detail below. A hydrodeoxygenated product can be produced. Alternatively, at least a portion of the naphtha product can also be discharged and used directly as a biofuel component and / or biochemical component.

  In further embodiments, optionally debutanized and / or depentanated naphtha products are sent to one or more additional distillation columns. Here, optionally debutanized and / or depentanated naphtha products are converted into light-light cycle oil (LLCO, sometimes also called heavy catalytic cracked gasoline (HCCG)); catalytic cracked gasoline (CCG, sometimes heart-cut). CCG); and light catalytic cracking gasoline (LCCG, sometimes also referred to as catalytic cracking overhead). In the present invention, light catalytic cracked gasoline is preferably a naphtha product in which at least 80% by weight, more preferably at least 90% by weight (at 0.1 MPa) boils in the range of 35 ° C. to less than 125 ° C. It is understood as a fraction. If desired, each of the light-light cycle oil, heavy catalytic cracked gasoline, and / or light catalytic cracked gasoline is independently hydrodeoxygenated as described below with respect to step (c). be able to.

  As indicated above, at least one fractionation of the one or more degradation products in step (b) yields one or more product fractions. At least one of the one or more product fractions obtained in step (b) is then hydrodeoxygenated in step (c) to produce one or more hydrodeoxygenated products.

  Examples of product fractions that can be obtained from step (b) and that can be hydrodeoxygenated in step (c) include naphtha products such as gasoline or diesel fraction; light cycle oil (LCO); heavy High quality cycle oil (HCO); slurry oil; fractions thereof and / or mixtures thereof.

  In a preferred embodiment, the one or more product fractions obtained in step (b) and then hydrodeoxygenated in step (c) are a naphtha product; a naphtha product fraction (such as heavy catalytic cracked gasoline, etc.). ); Light cycle oil (LCO); LCO fraction; and / or mixtures thereof.

  Preferably, the one or more product fractions obtained in step (b) and then hydrodeoxygenated in step (c) are at least 70% by weight, more preferably at least 80% by weight, most preferably at least at least 90% by weight (at 0.1 MPa) is composed of a fraction of decomposition products that boils in the range from 30 ° C. to less than 370 ° C. More preferably, the one or more product fractions obtained in step (b) and then hydrodeoxygenated in step (c) are at least 70% by weight, more preferably at least 80% by weight, most preferably At least 90% by weight (at 0.1 MPa) is composed of a fraction of decomposition products that boil in the range from 30 ° C. to less than 221 ° C.

  The one or more product fractions obtained in step (b) and then hydrodeoxygenated in step (c) may comprise one or more oxygen-containing hydrocarbons. Examples of such oxygen-containing hydrocarbons include ethers, esters, ketones, acids, and alcohols. In particular, the one or more product fractions may contain phenols and / or substituted phenols.

  Preferably, the one or more product fractions produced in step (b) and then hydrodeoxygenated in step (c) are based on the total weight of dry matter (ie, substantially free of water). 0.01 wt% or more, more preferably 0.1 wt% or more, even more preferably 0.2 wt% or more, most preferably 0.3 wt% or more, 20 wt% or less, more preferably 10 wt% or more. It has an elemental oxygen content in the range of up to 5% by weight, most preferably up to 5% by weight.

  In the present invention, hydrodeoxygenation means that in one or more product fractions containing oxygen-containing hydrocarbons, one or more product fractions are brought into contact with hydrogen in the presence of a hydrodeoxygenation catalyst. Is understood to reduce the concentration of oxygen-containing hydrocarbons. Oxygen-containing hydrocarbons that can be removed include acids, ethers, esters, ketones, aldehydes, alcohols (eg, phenols), and other oxygen-containing compounds.

  Hydrodeoxygenation is preferably a range of one or more product fractions in the presence of a hydrodeoxygenation catalyst in the range of 200 ° C or higher, preferably 250 ° C or higher, 450 ° C or lower, preferably 400 ° C or lower. A total pressure in the range of 10 bar absolute pressure (1.0 MPa) to 350 bar absolute pressure (35 MPa); and a hydrogen content in the range of 2 bar absolute pressure (0.2 MPa) to 350 bar absolute pressure (35 MPa). Pressure and contact with hydrogen.

  When the product fraction is light cycle oil (LCO) or a fraction thereof, hydrodeoxygenation is more preferably 30 bar absolute pressure (3.0 MPa) or more, most preferably 50 bar absolute pressure (5.0 MPa). Above, a total pressure in the range of 350 bar absolute pressure (35 MPa) or less, more preferably 300 bar absolute pressure (30 MPa) or less; and 20 bar absolute pressure (2.0 MPa) or more, most preferably 40 bar absolute pressure (4.0 MPa) The hydrogen partial pressure is in the range of 350 bar absolute pressure (35 MPa) or less, more preferably 300 bar absolute pressure (30 MPa) or less.

  When the product fraction is naphtha or a fraction thereof, hydrodeoxygenation is more preferably 10 bar absolute pressure (1.0 MPa) or more, most preferably 20 bar absolute pressure (2.0 MPa) or more and 100 bar absolute. Pressure (10 MPa) or less, more preferably total pressure in the range of 60 bar absolute pressure (6.0 MPa) or less; and 5 bar absolute pressure (0.5 MPa) or more, most preferably 10 bar absolute pressure (1.0 MPa) or more, 100 bar absolute pressure (10 MPa) or less, more preferably hydrogen partial pressure in the range of 60 bar absolute pressure (6.0 MPa) or less.

  The hydrodeoxygenation catalyst may be any type of hydrodeoxygenation catalyst known to those skilled in the art to be suitable for this purpose.

  The hydrodeoxygenation catalyst preferably includes one or more hydrodeoxygenation metals (preferably supported on a catalyst support). The catalyst support is preferably inert as a hydrodeoxygenation catalyst under hydrodeoxygenation conditions.

  The one or more hydrodeoxygenated metals are preferably selected from Group VIII and / or Group VIB of the Periodic Table of Elements. The hydrodeoxygenated metal can be present, for example, as a mixture, alloy, or organometallic compound.

  Preferably, the one or more hydrodeoxygenated metals are nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W), cobalt (Co), platinum (Pt), palladium (Pd), rhodium. (Rh), ruthenium (Ru), iridium (Ir), osmium (Os), copper (Cu), iron (Fe), zinc (Zn), gallium (Ga), indium (In), vanadium (V), and Selected from the group consisting of these mixtures. One or more metals can be present in elemental form; in the form of an alloy or mixture; and / or in the form of an oxide, sulfide, or other metal organic compound.

  Preferably, the hydrodeoxygenation catalyst in step (c) is a catalyst comprising tungsten, ruthenium, rhenium, cobalt, nickel, copper, molybdenum, alloys thereof, and / or mixtures thereof.

  Most preferably, the hydrodeoxygenation catalyst is selected from the group consisting of a rhodium-cobalt catalyst, a nickel-tungsten catalyst, a nickel-copper catalyst, a cobalt-molybdenum catalyst, and a nickel-molybdenum catalyst. Such rhodium-cobalt catalyst, nickel-tungsten catalyst, nickel-copper catalyst, cobalt-molybdenum catalyst, or nickel-molybdenum catalyst can include such metals supported on the inert catalyst support described above.

Where the hydrodeoxygenation catalyst includes a catalyst support, such catalyst support can be formed in the form of a sphere, ring, or other shaped extrudate. The catalyst support may include a refractory oxide or a mixture thereof, preferably alumina, amorphous silica-alumina, titania, silica, ceria, zirconia; or it may be inert such as carbon or silicon carbide. Ingredients can be included. For example, ZrO ₂ , CeO ₂ , CeO ₂ , and / or mixtures thereof are preferred. The catalyst support further includes zeolite compounds such as zeolite Y, zeolite β, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO-41, and ferrierite. Can be included.

Examples of suitable catalysts include: Rh / SiO ₂ ; RhCo / Al ₂ O ₃ ; Rh / CoSiO ₃ ; RhCo / SiO ₂ ; Co / SiO ₂ ; Rh / ZrO ₂ ; Rh / CeO ₂ ; Ni / SiO ₂ ; _{Ni / Cr 2 O 3; Ni} / Al 2 O 3; Ni / ZrO 2; Ni-Cu / Al 2 O 3; Ni-Cu / ZrO 2; Ni-Cu / CeO 2; Ni-Mo / Al 2 O 3 Ni—Mo / ZrO ₂ ; Co—Mo / Al ₂ O ₃ ; and Co—Mo / ZrO ₂ ; Preferably, the catalyst is Rh / Al ₂ O ₃ ; RhCo / Al ₂ O ₃ ; Rh / ZrO ₂ ; Rh / CeO ₂ ; Ni / Cr ₂ O ₃ ; Ni / Al ₂ O ₃ ; Ni / ZrO ₂ ; _{-Cu / Al 2 O 3; NiW} / Al 2 O 3; Ni-Cu / ZrO 2; Ru / C; Ni-Cu / CeO 2; Ni-Mo / Al 2 O 3; Ni-Mo / ZrO 2; Co Selected from the group consisting of: Mo / Al ₂ O ₃ ; Co—Mo / ZrO ₂ ; and / or mixtures thereof.

Rhodium on alumina (Rh / Al ₂ O ₃ ), rhodium-cobalt on alumina (RhCo / Al ₂ O ₃ ), nickel-copper on alumina (NiCu / Al ₂ O ₃ ), nickel-tungsten on alumina ( NiW _/ Al _{2 O} 3), cobalt on alumina - molybdenum _{(CoMo / Al 2 O 3)} , or alumina on nickel - molybdenum (NiMo / _Al 2 _{O 3)} hydrodeoxygenation catalysts containing most preferred.

  If the one or more product fractions also contain one or more sulfur-containing hydrocarbons, it may be advantageous to use a sulfurized hydrodeoxygenation catalyst. When sulfiding a hydrodeoxygenation catalyst, the catalyst can be sulfided in-situ or ex-situ. Such in-situ or ex-situ sulfidation can be performed by any method known to those skilled in the art to be suitable for in-situ or ex-situ sulfidation. In the case of in-situ sulfidation, a sulfur source, usually hydrogen sulfide or a hydrogen sulfide precursor, is preferably fed to the hydrodeoxygenation catalyst prior to operation of the process in the hydrodeoxygenation reactor. . Furthermore, it may be advantageous to add a small amount of hydrogen sulfide during operation of the hydrodeoxygenation process to keep the catalyst in a sufficiently sulfurized state.

  In addition to hydrodeoxygenation, step (c) can include additional steps if desired or necessary. For example, if desired, step (c) can further include hydrodesulfurization, hydrodenitrogenation, hydrocracking, and / or hydroisomerization of one or more product fractions. Hydrodesulfurization can reduce the concentration of sulfur-containing hydrocarbons. Hydrodenitrification can reduce the concentration of nitrogen-containing hydrocarbons. Hydroisomerization can increase the concentration of branched hydrocarbons. Hydrocracking can further break down the product into smaller compounds.

  Such hydrodesulfurization, hydrodenitrogenation, hydrocracking, and / or hydroisomerization can be performed before, after, and / or simultaneously with hydrodeoxygenation.

  Hydrodeoxygenation can be performed in any type of reactor known to those skilled in the art to be a step for the hydrodeoxygenation process. Preferably, a fixed bed reactor, a trickle bed reactor, a boiling bed reactor or a fluidized bed reactor is used. In a preferred embodiment, a weight space velocity of 0.2 or more and 4.0 kg / L · hour or less is used.

  In step (c), one or more hydrodeoxygenation products can be obtained. These one or more hydrodeoxygenation products can be used as one or more biofuel components and / or biochemical components. A biofuel component is understood in the present invention as a component that may be useful in the production of biofuel. A biochemical component is understood in the present invention as a component that may be useful in the production of biochemical materials.

  Preferably, the one or more hydrodeoxygenation products have an elemental oxygen content of 0.03% by weight (300 ppmw) or less, more preferably 0.01% by weight or less. Most preferably, the one or more hydrodeoxygenation products are substantially free of oxygen-containing hydrocarbons and / or substantially free of elemental oxygen.

  In a preferred embodiment, the one or more hydrodeoxygenation products produced in step (c) can be blended with one or more other components to produce a biofuel and / or biochemical material. Examples of one or more other ingredients that can be blended with one or more hydrodeoxygenation products include antioxidants, corrosion inhibitors, ashless cleaners, anti-fogging agents, dyes, lubricity An improver and / or an inorganic fuel component may be mentioned.

  Alternatively, one or more hydrodeoxygenation products can be used in the production of biofuel components and / or biochemical components. In such a case, the biofuel component and / or biochemical component produced from one or more hydrodeoxygenation products is then blended with one or more other components (listed above) to biofuel. And / or biochemical materials can be produced.

  A biofuel or biochemical substance is understood in the context of the present invention as a fuel or chemical substance derived from an at least partly renewable energy source.

  In FIG. 1, an embodiment according to the present invention is shown. In FIG. 1, a wood part (102) is fed into a heat drying unit (104) in which the wood is heat dried to produce heat dried wood (108), from the top a gaseous product (106). Get. The heat-dried wood (108) is sent to a pulverizer (110) where the heat-dried wood is pulverized into a pulverized heat-dried wood (112). The micronized heat-dried wood (112) is then sent to a mixer or extruder (114) where it is mixed with a mixture of vacuum gas oil and long residue as a fluid hydrocarbon co-feed (116) to provide a feed mixture ( 118) is produced and fed into the bottom of the FCC reactor riser (120). In the FCC reactor riser (120), the feed mixture (118) is contacted with the newly regenerated catalytic cracking catalyst (122) at the catalytic cracking temperature. The spent catalytic cracking catalyst (128) and the mixture of cracked product (124) produced are separated in a separator (126). Spent catalytic cracking catalyst (128) is sent to regenerator (130) where it is regenerated and recycled to the bottom of the riser reactor as part of the regenerated catalytic cracking catalyst (122). The decomposition product (124) is sent to a separator (132). In the separator (132), the decomposition product (124) is separated into, for example, a slurry oil-containing fraction (134), a heavy cycle oil-containing fraction (136), a light cycle oil-containing fraction (138), and a naphtha-containing fraction (140). Fractionation into several product fractions such as At least a portion of the naphtha-containing fraction (140) is sent to a hydrodeoxygenation reactor (142) where it is hydrodeoxygenated over a nickel-molybdenum catalyst on alumina for hydrodeoxygenation product (144). Is generated. The hydrodeoxygenated product can be blended with one or more other additives to produce a biofuel suitable for use in automotive engines.

  In FIG. 2, another embodiment according to the present invention is shown. In FIG. 2, a wood part (202) is fed into a heat drying unit (204) in which the wood is heat dried to produce heat dried wood (208), from the top a gaseous product (206). Get. The heat-dried wood (208) is sent to a pulverizer (210) where the heat-dried wood is pulverized into a pulverized heat-dried wood (212). Micronized heat-dried wood (212) is fed directly into the bottom of the FCC reactor riser (220). Further, a long residue (216) is fed to the bottom of the FCC reactor riser (220) at a location downstream of the introduction of finely divided heat-dried wood (212). In the FCC reactor riser (220), the finely divided heat-dried wood (212) is newly regenerated at the catalytic cracking temperature in the presence of long residue as a fluid hydrocarbon co-feed (216). Contact with catalyst (222). A mixture of spent catalytic cracking catalyst (228) and cracked product (224) produced is separated in separator (226). Spent catalytic cracking catalyst (228) is sent to regenerator (230) where it is regenerated and recycled to the bottom of the riser reactor as part of the regenerated catalytic cracking catalyst (222). The decomposition product (124) is sent to a separator (232). In the separator (232), the cracked product (224) is separated into, for example, a slurry oil-containing fraction (234), a heavy cycle oil-containing fraction (236), a light cycle oil-containing fraction (238), and a naphtha-containing fraction (240). Fractionation into several product fractions such as At least a portion of the naphtha-containing fraction (240) is sent to a hydrodeoxygenation reactor (242) where it is hydrodeoxygenated over a nickel-molybdenum catalyst on alumina for hydrodeoxygenation product (244). Is generated. The hydrodeoxygenated product can be blended with one or more other components to produce a biofuel suitable for use in an automobile engine.

  The invention is further illustrated by the following non-limiting examples.

  The invention will now be further illustrated by the following non-limiting examples. In the following experiments, elemental carbon and hydrogen analyzes are performed according to ASTM method D5291 unless otherwise indicated; elemental nitrogen analysis is performed on ASTM method D5762 (>) on an Antek 9000 instrument unless otherwise indicated. Analysis for ASTM 4629 (for less than 100 ppm nitrogen); elemental oxygen analysis on Eurovector EA3000 instrument (commercially available from Eurovector) or Elementar GmbH Vario Cube instrument unless otherwise indicated Elemental sulfur analysis was performed by burning ASTM D5453 with UV fluorescence detection on an Antek 9000 instrument, unless otherwise indicated. Gas chromatography and oxygen content of the feed were determined by ASTM D5599-95 unless otherwise indicated.

Example 1-Production of a mixture of ground heat dried poplar wood and fluid hydrocarbon feed:
Poplar wood chips were heat dried at 250 ° C. for 6 hours. These were finely pulverized at 400 rpm for 4 hours using a Retch PM400 ball mill to prepare a pulverized heat-dried wood material. The ground heat-dried poplar wood had an apparent bulk density of 0.42 g / mL and an average particle size distribution of 36 μm (measured with a Horiba LA950 laser scattering particle size distribution analyzer). The ground heat-dried poplar wood was dried at 105 ° C. throughout the day. Next, pulverized heat-dried poplar wood (MTPW) was added to the fluid hydrocarbon feed (HF) in the weight ratio shown below.

(1a) 0 wt% MTPW and 100 wt% HF;
(1b) 5 wt% MTPW and 95 wt% HF;
(1c) 10% by weight MTPW and 90% by weight HF;
(1d) 20 wt% MTPW and 80 wt% HF.

  A mixture that can be pumped by shaking and stirring the above combination of ground heat-dried poplar wood and fluid hydrocarbon feed for 1 hour at room temperature and mixing / chopping at 80 ° C. for 1 hour using an Inline Ultra Turrax extruder Gave.

  The boiling range distribution of the fluid hydrocarbon feed is given in Table 1. Elemental analysis of ground heat dried poplar wood and fluid hydrocarbon feed is given in Table 2. The ground heat-dried poplar wood was dried to remove water prior to analysis.

Example 2 Fluid catalytic cracking of a mixture of fluid hydrocarbon feed and ground heat dried poplar wood at 520 ° C .:
A mixture of ground heat-dried poplar wood and fluid hydrocarbon feed listed as 1a, 1b, 1c, and 1d as feed mixture from a stirred feed container at 60 ° C. into the fluidized bed of a MAT-5000 fluid catalytic cracking unit. Injected.

  Each mixture was tested in a separate experiment. Each experiment used 7 catalyst / feed weight ratios, ie, 3, 4, 5, 6, 6.5, 7, and 8 catalyst to feed (catalyst / feed) weight ratios. Seven experiments were included.

  Each experiment was performed as follows.

10 g of FCC equilibrium catalyst (ie catalytic cracking catalyst) containing ultrastable zeolite Y having the composition shown in Table 3 was constantly fluidized with nitrogen. An exact known amount of feed was injected and then flushed through the tube with nitrogen into the fluidized catalyst bed during a 1 minute run time. The fluidized catalyst bed was maintained at 520 ° C. The liquid product (also called total liquid product (TLP)) was collected in a glass receiver at -18 to -19 ° C. The catalytic cracking catalyst was then stripped with nitrogen. The gas produced during such stripping was weighed and analyzed online by gas chromatograph (GC). Thereafter, the catalytic cracking catalyst was regenerated in-situ at 650 ° C. in the presence of air. Cork in the reproduction is converted to CO _2, which was quantified by online infrared measurement. After regeneration, the reactor was cooled to the decomposition temperature and a new injection was started. One cycle including all catalyst / oil ratios took about 16 hours.

  Seven experiments were used to generate extrapolated results for each catalyst / feed weight ratio and each conversion. From these extrapolated results, yields for different product fractions were determined and are shown in Table 4. Elemental analysis of the total liquid product is shown in Table 5.

  As shown in Table 5, TLP still contains elemental oxygen. Oxygen can be removed by hydrodeoxygenation of the total liquid product shown in Table 5.

Example 3-Determination of biocarbon content in the total liquid product:
The biocarbon content of the total liquid product obtained by catalytic cracking of a feed mixture containing 20% by weight ground heat-dried poplar wood and 80% by weight fluid hydrocarbon feed was determined by carbon isotope analysis according to ASTM 6866. Measurements showed that about 38% by weight of elemental oxygen (also referred to as biocarbon) present in the pulverized heat-dried poplar wood was present in the catalytically cracked total liquid product. The total mass balance (heated dry wood and fluid hydrocarbon feed) for any of the above experiments is also required to be in the range of 98-102% by weight, which puts the hot dry wood feed into the reactor in its entirety. Indicates that it has been introduced. Variations in mass balance are experimental variations normally observed in FCC experiments in the reactor used.

Example 4-Hydrodeoxygenation of all liquid products:
A feed mixture comprising 18 wt.% Ground heat-dried poplar wood and 82 wt.% Fluid hydrocarbon feed having the properties shown in Tables 1 and 2 at 520 ° C. using a catalyst / feed weight ratio of 3 In a MAT-5000 fluid catalytic cracking unit, the catalytic cracking catalyst described in Example 2 was used for catalytic cracking to produce a total liquid product (TLP).

In a 500 mL autoclave (Ernst Haage), 10 g of this total liquid product is diluted with 150 mL of dodecane and then presulfided 0. 5% containing 3.5 wt% nickel and 15 wt% molybdenum on alumina. Blended with 77 g hydrodeoxygenation catalyst (DN3531, commercially available from Criterion). The autoclave with gaseous mixture of hydrogen 1% hydrogen sulfide _{(H 2)} in _(H 2 S) was pressurized to 60 bar (6.0 MPa). The autoclave was then heated to 300 ° C. (at a rate of 25 ° C./min) to obtain a final pressure of 87 bar (8.7 MPa). After treating the above in an autoclave for about 2 hours, the autoclave was cooled and depressurized. Samples were taken from the total liquid product for elemental analysis before and after hydrodeoxygenation. Table 6 shows the results of elemental analysis. Elemental analysis of the hydrodeoxygenated total liquid product showed that oxygen was substantially absent.

Claims (14)

(A) in a catalytic cracking reactor, the solid biomass material and the fluid hydrocarbon feed are contacted with a catalytic cracking catalyst at a temperature greater than 400 ° C. to produce one or more cracked products;
(B) separating the one or more decomposition products produced in step (a) to produce one or more product fractions;
(C) hydrodeoxygenating one or more product fractions produced in step (b) to produce one or more hydrodeoxygenated products;
A method of converting solid biomass material comprising:   The method of claim 1, wherein the solid biomass material is selected from the group consisting of wood, sawdust, firewood, turf, bagasse, corn stover, and / or mixtures thereof.   The method according to claim 1 or 2, wherein the solid biomass material in step (a) is a heat-dried solid biomass material.   The solid biomass material in step (a) has an average particle size in the range of 5 μm to 5000 μm as measured using a laser scattering particle size distribution analyzer. Method.   The solid biomass material in step (a) is obtained by reducing the particle size of the solid biomass material (optionally heat-dried) in the presence of liquid hydrocarbons. The method described in 1.   6. The method of claim 5, wherein the liquid hydrocarbon is the same as the fluid hydrocarbon co-feed in step (a).   Fluid hydrocarbon co-feed materials are straight-run gas oil, flash distillate, vacuum gas oil, coker gas oil, atmospheric residue (long residue), vacuum residue (short residue), naphtha, gasoline, diesel, kerosene, and liquefaction 7. A method according to any one of claims 1 to 6, selected from the group consisting of petroleum gas.   8. A method according to any one of the preceding claims, wherein the fluid hydrocarbon co-feed comprises 8 wt% or more elemental hydrogen based on the total weight of the fluid hydrocarbon co-feed on an anhydrous basis.   9. A process according to any one of the preceding claims, wherein the fluid hydrocarbon co-feed and the solid biomass material are mixed prior to introduction into the catalytic cracking reactor.   9. A process according to any one of the preceding claims, wherein the fluid hydrocarbon cofeed and the solid biomass material are added separately to the catalytic cracking reactor.   11. The one or more degradation products obtained in step (a) comprise 0.01% by weight or more elemental oxygen based on the total weight of the one or more degradation products on an anhydrous basis. The method of any one of these.   12. The one or more product fractions obtained in step (b) comprise 0.01% by weight or more elemental oxygen based on the total weight of the one or more product fractions on an anhydrous basis. The method of any one of these.   One or more product fractions obtained in step (b) and hydrodeoxygenated in step (c) are at least 70%, more preferably at least 80%, most preferably at least 90% by weight of the fraction. The method according to any one of claims 1 to 12, wherein the method comprises a fraction of decomposition products that boils in the range of 30 ° C to less than 370 ° C.   14. One or more hydrodeoxygenation products comprising blending one or more hydrodeoxygenation products with one or more other ingredients to produce a biofuel and / or biochemical material. Method.

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